JPH03115363A - Hexakisazo compound and recording liquid containing same - Google Patents

Abstract

NEW MATERIAL:A compd. of formula I (wherein Q<1> to Q<4> are each a benzene or naphthalene ring capable of being substituted by an amino group, etc.; X is Cl, OH, etc.; M is an alkali metal, ammonium, etc.; and m and n are each 0 or 1, and m+n=1). EXAMPLE:A compd. of formula II. USE:A dye useful as a recording material in a recording liq. for an ink jet system. PREPARATION:First, an amine of the formula Q<1>-NH2, is diazotized and then coupled with an amine of the formula, H-Q<2>-NH2. The resulting monoazo compd. is diazotized and then coupled with a naphthol of formula III to give a disazo compd. of formula IV, which is further diazotized and coupled with phenylenediaminesulfonic acid to give a trisazo compd. of formula V. The trisazo compd. is finally reacted with 2,4,6-trichlorotriazine.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a novel recording liquid, particularly a method for recording by ejecting it from a fine ejection port (ejection orifice) provided in a print head and flying it as droplets. The present invention relates to a recording liquid suitable for a recording method that performs this and a novel azo compound suitable for use in the recording liquid.

[Conventional technology]

BACKGROUND ART Writing instruments (fountain pens, felt pens) for recording on recording materials such as paper have conventionally used inks prepared by dissolving various dyes in water or other organic solvents.

Furthermore, in the so-called inkjet recording method, in which recording is performed by ejecting liquid in the recording head from an ejection orifice using vibrations by a piezo vibrator or electrostatic attraction due to the application of high voltage, various dyes are dissolved in water or organic solvents. It is known that compositions are used. However, compared to inks for general stationery such as fountain pens and felt-tip pens, inkjet recording liquids have many characteristics and are required to meet stricter conditions. Such an inkjet recording method uses droplets of a recording liquid called ink.
Recording is performed by making the particles fly and attaching them to the recording material. The basic components of such a recording liquid include a recording agent (dye or pigment is used) and a liquid medium for dissolving or dispersing it (water, various types of solvents, or mixtures thereof are used), and if necessary, Various additives are added.

There are various types of such recording methods depending on the method of generating droplets and the method of controlling the flight direction of the droplets. An example thereof is shown in Japanese Patent Publication No. 60-33145.

Conventionally, as this type of recording liquid, for example, Japanese Patent Publication No. 61-18
No. 590, Special Publication No. 61-18947, Special Publication No. 18947, Special Publication No. 61-3
No. 6875, Special Publication No. 38225, Special Publication No. 1982-
38747 and Japanese Patent Publication No. 61-55545 are known. The preferred conditions for this type of recording liquid are (11) Liquid physical properties (viscosity, surface tension, conductivity, etc.) that match the ejection conditions (piezoelectric element drive voltage, drive frequency, orifice shape and material, orifice diameter, etc.). have.

(2) Stable for long-term storage and should not cause clogging.

(3) The dots should be fixed quickly on the recording material (paper, film, etc.) and the periphery of the dots should be smooth with little bleeding.

(4) The color tone of the printed image is clear and the density is high.

(5) The printed image has excellent water resistance and light resistance.

(6) The recording liquid should not corrode surrounding materials (containers, connecting tubes, sealing materials, etc.).

(7) It must be safe in terms of odor, toxicity, flammability, etc.

etc.

It is quite difficult to simultaneously satisfy the above characteristics. The prior art described above was unsatisfactory in this respect.

[Problem to be solved by the invention]

Since the recording liquid used for such recording purposes is basically composed of a dye and its solvent, the above-mentioned characteristics of the recording liquid are largely influenced by the inherent properties of the dye. Therefore, selecting a dye so that the recording liquid has the above characteristics is an extremely important technique in this technical field.

The present invention was completed by finding a dye suitable for the recording liquid used for this purpose.

[Means to solve the problem]

That is, the present invention provides the following formula N) C1) (wherein Ql, C4, C3, and C4 are benzene rings or naphthalene rings optionally substituted with an amino group, an acylamino group, an alkyl group, an alkoxy group, or a 503M group) , X represents a chloro atom, hydroxyl group, amine group or hydroxyethylamino group, M represents an alkali metal, ammonium or amine salt, m and n each represent kO or 1. However, m + n = l. ), a recording agent which is a component for forming a recorded image, and a solvent for dissolving or dispersing this recording agent, in which the above-mentioned -Funenin (.) is used as a recording agent. The present invention relates to a recording liquid characterized by containing at least one dye represented by 1).

In the above formula, the acyl group of the acylamino group which is a substituent of the benzene ring or naphthalene ring represented by Ql, C2, C3, C4 includes an alkylcarbonyl group having 2 to 5 carbon atoms or a benzoyl group, Examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms such as a methyl group, and examples of the alkoxy group include alkyl groups having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group. In addition, the amine salts represented by M include mono-, di-, tri-(lower alkyl) amines, mono-, di-, tri-(hydroxy-lower alkyl) amines, or amines substituted with both lower alkyl groups and hydroxy lower alkyl groups. etc.

The compound of the present invention can be produced by the following method.

That is, the following - Sailor [n] Q' - Nl2 ... [■] [Q in the formula
' is the same as the above definition] After diazotizing the amines shown by using sodium nitrite etc. in a mineral acid such as hydrochloric acid or sulfuric acid, the following - Shipman () % formula % [) [In the formula, 02 is Same as the above definition] By coupling with the amines shown by the following - Shipman [■] Q' N=N Q'' Nl2 ...
(2) A monoazo compound represented by the formula [wherein Q1 and C2 are the same as defined above] is obtained.

After diazotizing the obtained monoazo compound using sodium nitrite or the like in a mineral acid such as hydrochloric acid or sulfuric acid, a naphthol represented by the following - Shipman [V] 503M [where M is the same as defined above] By coupling with, a disazo compound represented by the following -Funenin () [in the formula, Q', C2, and M are the same as defined above] is obtained.

These disazo compounds are diazotized in a mineral acid such as hydrochloric acid or sulfuric acid or in an organic acid such as acetic acid using sodium nitrite, etc., and then coupled with phenylenediamine sulfonic acid to form the following - Shipman [ [2] A trisazo compound represented by [2] is obtained.

[■]

The compound of the present invention is obtained by reacting this trisazo compound (in the formula, Q I , C2, M are the same as defined above) with 2,4.6-)lychlortriazine in water. By the way, the compound of the present invention may also be obtained by reacting a mixture of two or more compounds having different substituents or positions of the trisazo compound represented by formula [■] with 2.4.6-dolychlortriazine. Okay, after reacting the compound of formula [■] above in the first stage of the reaction,
It may be a product obtained by reacting a compound of the general formula [■] in which the substituent group or its position is different from that in the previous stage.

The compound of the present invention is usually obtained in the form of a mixture of isomers, as shown in the example of the compound in item 1 below, but this can be fractionated by conventional methods such as chromatographic separation.

Specific examples of the compounds of the present invention are shown in Table 1 below.
Hereafter, only representative structures among the isomers will be described. Furthermore, the maximum absorption wavelength in water was measured as a mixture.

Table (Continued) Table (Continued) 1st Table (Continued) Table (Continued) When the above-mentioned compound, that is, dye, is used in the recording liquid of the present invention, the content thereof is determined by the types of liquid medium components, the characteristics required for the recording liquid, etc. Although it is determined depending on the total weight of the recording liquid, it is generally in the range of 0.1 to 20% by weight, preferably 0.5 to 15%, and more preferably 1 to 10%. . Of course, these dyes can be used alone or in combination of two or more, or in combination with various dyes such as other direct dyes and acid dyes, using the dye as an essential component.

As a liquid medium component for composing the recording liquid of the present invention, water or a mixture of water and various water-soluble organic solvents is used. Examples of water-soluble organic solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol,
Isopropyl alcohol, n-butyl alcohol, 5e
c-butyl alcohol, tert-butyl alcohol,
Alkyl alcohols having 1 to 4 carbon atoms such as isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; tetrahydrofuran,
Ethers such as dioxane; nitrogen-containing heterocyclic ketones such as N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Alkylene groups such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2゜6-hexandriol, thiodiglycol, hexylene glycol, diethylene glycol, etc.
Examples include alkylene glycols containing 6 carbon atoms; glycerin; and lower alkyl ethers of polyhydric alcohols such as ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, and triethylene glycol monomethyl (or ethyl) ether. The content of the water-soluble organic solvent in the recording liquid is generally 10 to 90% by weight based on the total weight of the recording liquid.
Preferably 10-70%, more preferably 10-50%
The range of

The content of water is determined within a wide range depending on the type of solvent component, its composition, and the desired characteristics of the recording liquid, but it is determined that the water content is 10% by weight based on the total weight of the recording liquid.
~90%, preferably 10-70%, more preferably 1
The range is 0 to 50%.

The recording liquid of the present invention prepared from such components has excellent recording characteristics (signal response, stability of droplet formation, ejection stability, ejection stability after a long period of recording interruption) and storage stability. It is well-balanced and excellent in terms of properties, fixability to recording materials, and light resistance, weather resistance, and water resistance of recorded images. In order to further improve such properties, various conventionally known additives may be further added.

For example, viscosity modifiers such as polyvinyl alcohol, celluloses, and water-soluble resins; cationic, anionic, or nonionic surfactants; surface tension modifiers such as jetanolamine and triethanolamine; pH modifiers using buffers; Antifungal agents and the like can be mentioned.

Further, in order to prepare a recording liquid used in an inkjet recording method of a type in which the recording liquid is charged, a resistivity adjuster such as an inorganic salt such as lithium chloride, ammonium chloride, or sodium chloride is added.

Note that when applied to an inkjet system in which recording liquid is ejected by the action of thermal energy, thermal physical property values (eg, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted.

〔Example〕

The present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless the gist of the invention is exceeded.

Example 1 Preparation of the compound shown in Table 1 (1) (11) Preparation of the first diazo liquid 2-Amino-naphthalene-4,8-disulfonic acid 30.
2 g to 3% hydrochloric acid 60 Qm7! and stirred for 3 hours to form a uniform slurry. Add 400g of ice to this and
Cooled to ℃. An aqueous solution of 7.3 g of sodium nitrite dissolved in 73 ml of water was added to this slurry. Then 3℃
After diazotization by stirring for 1 hour, 3 g of sulfamic acid
was added to eliminate the remaining sodium nitrite to obtain a first diazo solution.

(2) First cambling 15.3 g of 2.5-dimethoxyaniline CH3 was added to 450 ml of water and stirred for 2 hours to form a uniform slurry. To this, add 300 g of ice, the first diazo solution obtained in fl) and 20 ml of 25% strength soda,
After coupling was performed by stirring at a temperature of 0 to 3° C. and a pH of 2 to 3 for 15 hours, 200 g of common salt was added to perform salting out. The precipitated monoazo compound was filtered, washed with 500 mβ of 10% saline, and dried to obtain 41.0 g of the following monoazo compound.

(3) Production of second diazo liquid 23.3 g of the monoazo compound obtained in the above (2) was
After adding 410 mff of % hydrochloric acid and stirring for 5 hours to obtain a uniform slurry, 300 g of ice was added and the mixture was cooled to 3°C. An aqueous solution of 3.8 g of sodium nitrite dissolved in 38 mJ of water was added to this slurry. Next, after diazotization by stirring at 3° C. for 10 hours, 1 g of sulfamic acid was added to eliminate remaining sodium nitrite to obtain a second diazo solution.

(4) Second coupling After adding 12.0 g of 1-hydroxy-7-amino-naphthalene-3-sulfonic acid to 460 m6 of water, add 800 g of ice, the second diazo liquid obtained in (2) above, and 25
Add 55mg of sodium hydroxide to pH 8~10 and temperature 2~
Coupling was performed at 5°C.

After stirring for 5 hours at the same temperature and pH, 250 g of salt was added.
was added to perform salting out. The precipitated compound was filtered, washed with 300 ml of 10% brine, and dried to obtain 31.3 g of the following disazo compound.

(5) Production of third diazo liquid 19.6 g of the disazo compound fIJ obtained in (4) was added to 400 ml of 3% hydrochloric acid and 100 ml of acetic acid, stirred for 3 hours to make a uniform slurry, and then 300 g of ice was added and the mixture was heated to 3°C. It was cooled to An aqueous solution of 1.8 g of sodium nitrite dissolved in 20 ml of water was added to this slurry. Then at 3℃
After diazotization by stirring for 4 hours, 0.5 g of sulfamic acid
was added to eliminate the remaining sodium nitrite to obtain a third diazo solution.

(6) Third coupling 1.3-diamino-benzene-4-sulfonic acid 4.7 g
After adding to 100mj2 of water, add 50g of ice to this and add 3
Cooled to ℃. Next, the third diazo liquid obtained in the above (5) was added and the mixture was stirred at a temperature of 2 to 5° C. for 10 hours to perform coupling, and then 250 g of common salt was added to perform salting out.

After filtering the precipitated compound, 20% saline solution 4QQm
Wash with ff, dry and prepare the following trisazo compound 18.
6 g was obtained.

(7) Dimerization 9.3 g of the trisazo compound obtained in (6) above was added to 40 Q of water.
ml, 60 g of ice was added and the mixture was cooled to 15°C.

Next, 1.7 g of 2,4.6-dolychlortriazine was added, and the mixture was reacted at 106 to 20°C for 5 hours. At this time, 35 mjl of 1% strength soda! was added to maintain the pH at 6-7.

Next, 9.3 g of the trisazo compound obtained in (6) was further added and reacted in the same manner as above at 406-50°C and pH 6-7 for 7 hours. Furthermore, 3 Q ml of 28% aqueous ammonia was added to this reaction solution, and the mixture was heated at 70° to 80°C for 2 hours.
Time reacted.

After the reaction solution was cooled to room temperature, 40 g of common salt was added, and the precipitate was filtered and washed with 10% brine.

The obtained x7 cake was desalted by a reverse osmosis membrane method and dried to obtain 14.6 g of the desired mixture of compounds represented by the above structural formulas 1-1 to 1-4.

Example 2 Composition of recording liquid Ion-exchanged water (hereinafter abbreviated as water) 71 parts by weight diethylene glycol 25 Dye mixture of Table 1, column 1 4 (The mixture obtained in Example 1 above was used as it was.) Each of the above The components were thoroughly mixed and dissolved in a container, filtered under pressure through a Teflon filter with a pore size of 1 μm, and then degassed using a vacuum pump to obtain a recording liquid.

Using the obtained recording liquid, an on-demand recording head (discharge orifice diameter 50μ, piezoelectric vibrator drive voltage 60V, frequency 4k) discharges the recording liquid using a piezoelectric vibrator.
Hz), the following (TI) to (T
, ) were investigated, and good results were obtained in both cases.

('r+) Long-term storage stability of the recording liquid: Even after the recording liquid was sealed in a glass container and stored at -30°C and 60°C for 6 months, no precipitation of insoluble matter was observed, and the physical properties and color tone of the liquid did not change. There was no change.

(T2) Ejection stability: Continuous ejection was performed for 24 hours in an atmosphere at room temperature, 5° C., and 40° C. Under all conditions, stable high-quality recording was possible from beginning to end.

(T3) Ejection response: Intermittent ejection for 2 seconds and ejection after being left for 2 months were investigated, and in both cases, there was no clogging at the tip of the orifice (stable and uniform recording was achieved).

(T4) Quality of recorded images: The recorded images had high density and were clear. After three months of exposure to room light, the density decrease was less than 1%, and when immersed in water for 1 minute, there was very little blurring of the image.

(T.) Fixability on various recording materials; After 15 seconds of printing with the recording materials listed in the table below, the printed area was rubbed with a finger to determine the presence or absence of image shift and bleeding. All of them exhibited excellent fixing properties with no image shift or blurring.

However, the name of the recording material is the product name.

Example 3 Composition of recording liquid Water N-methyl-2-pyrrolidone 62 parts by weight 15 Diethylene glycol 19 Dye (mixture) of 3 in Table 1 4 A recording liquid having the above composition was prepared in the same manner as in Example 2. The on-demand type multi-head (discharge orifice diameter 35μ,
Heat generating resistor resistance value 150Ω, drive voltage 30V, frequency 2
Similar to Example 2, (T,) to (T,) were investigated using a recording device having a frequency of kHz (kHz), and excellent results were obtained in all the investigation experiments.

Example 4 Composition of recording liquid Water 45 parts by weight Ethylene glycol 20 1,3-dimethyl-2-imidazolidinone 30 Dye (mixture) of grade 7 in Table 1 5 The above composition was prepared in the same manner as in Example 2. An on-demand type multi-head (discharge orifice diameter 35μ, heating resistor resistance value 150Ω, drive voltage 3
Similar to Example 2, (T,) to (T,) were investigated using a recording device having a voltage of 0 V and a frequency of 2 kHz, and excellent results were obtained in all the investigation experiments.

Example 5 Composition of recording liquid Water 60 parts by weight Diethylene glycol 36 Dye (mixture) of grade 6 in Table 1
4 A recording liquid having the above composition was prepared in the same manner as in Example 2, and an on-demand type multi-head (discharge orifice diameter Similar to Example 2, (TI) to (T
5) was investigated, and excellent results were obtained in all the investigation experiments.

Example 6 Composition of recording liquid Water 66 parts by weight Diethylene glycol monomethyl ether 30 Dye (mixture) of 2 in Table 1 4 A recording liquid having the above composition was prepared in the same manner as in Example 2, and recording in the recording head was performed. On-demand type multi-head that generates droplets by applying thermal energy to the liquid and performs recording (discharge orifice diameter 35μ, heating resistor resistance 150Ω, drive voltage 3)
Similar to Example 2, ('r+) to (T,) were investigated using a recording device having a voltage of 0 V and a frequency of 2 kHz, and excellent results were obtained in all the experimental experiments.

Examples 7 and 8 Recording liquids having the compositions shown in 7 and 8 below were prepared in the same manner as in Example 2. These compositions were filled into felt-tip pens and written on medium-quality paper (Hakubotan Nihonshu Paper ■) to examine water resistance and writability after the cap was removed and left for 24 hours.

The recording liquid of this example was excellent in both water resistance and writability after standing.

Composition of recording liquid of Example 7 Water 71 parts by weight Diethylene glycol 25 Dye (mixture) of Grade 4 in Table 1
4 Composition of the recording liquid of Example 8 Water 45 parts by weight Ethylene glycol 20 N-methyl-2-pyrrolidone 30 Dye (mixture) of Level 5 in Table 1 5 [
[Effects of the Invention] By using the hexakisazo compound of the present invention, physical property values such as viscosity and surface tension are within appropriate ranges, and a recorded image with sufficiently high density can be obtained without clogging the fine discharge orifice. It does not cause changes in physical properties or precipitation of solids during storage, can record on a variety of materials without limiting the type of recording material, has a high fixing speed, and has excellent water resistance, abrasion resistance, and resolution. A recording liquid that gives a clear image is obtained.

Claims (2)

[Claims] (1) A hexakisazo compound represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Q^1, Q^2, Q^3, Q^4 are amino groups, acylamino groups, alkyl groups, alkoxy groups, or SO_3
represents a benzene ring or naphthalene ring which may be substituted with an M group, X represents a chloro atom, hydroxyl group, amino group or hydroxyethylamino group, M represents an alkali metal, ammonium or amine salt, m and n Each represents 0 or 1. However, m+n=1. ) (2) In a recording liquid containing a recording agent which is a component for forming a recorded image and a solvent for dissolving or dispersing this recording agent, a dye represented by the following general formula [I] is used as a recording agent. A recording liquid characterized by containing at least one of the following. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, Q^1, Q^2, Q^3, Q^4 are amino groups, acylamino groups, alkyl groups, alkoxy groups, or SO_3
Represents a benzene ring or naphthalene ring which may be substituted with an M group, X represents a chloro atom, hydroxyl group, amino group or hydroxyethylamino group, M represents an alkali metal, ammonium or amine salt, m and n represent Each represents 0 or 1. However, m+n=1. )